Colored photographic layers



Patented Oct. 10, 1950 COLORED PHOTOGRAPHIO LAYERS Laurent Aloys Van der Auwera, Mortsel-Antwerp,

and Andre Emile Van-Dormael, Heverlee-Lou- I vain, Belgium, assignors to Geva er t 1Photo Producten N. V., 'Mortsel-Antwerp, Belgium, a

company of Belgium No Drawing. Application May 13, 1947, Serial No. 747,846. In the Netherlands May 21, 1946 5 Claims. 1-

This invention relates to colored photographic layers, especially anti-halation and filter layers. There are some qualities required for usable colored photographic layers: Their absorption range must be adapted to the optical sensitization of the emulsion; they must decolorize very quickly, completely and irreversibly in weak alkaline developing baths. In addition, their decomposition products should not influence the development or photographic properties of the emulsion. Nor should mechanic influences detach thedyestuffitself or injure the thin layer. Fingers, when touching and even when wet, shall not become colored. It is desirable that the absorption of the colored layer be sufficiently high so that the effect in view may be obtained with a thin color layer.

The prior colored photographic layers, however, do not show all of the above indicated properties. For instance, diphenyl methane dyestufis were employed heretofore.

It has also been suggested to use basic azomethine dyestuffs wherein the methine group forms part of a heterocyclic .ring, and to react'these dyestuffs with organic acids containing at least one COOH or OH gIOllp suitable for salt formation. Such methods are disclosed in the co-pending application of Rene Adriaan Stevens, Laurent Aloys Van der Auwera, and Dsir Maria Aloysius Van Goethem, Serial No. 741,684, filed April 15, 19431; and in the co-pending application of Jacob Joseph Jennen, Serial No. 747,845, filed May 13, 1947.

It is among the objects of our present invention to generally improve colored photographic layers and to provide a new process for the manufacture of same.

An important object of this invention is to provide colored photographic layers meeting the above requirements.

Another object of our invention is to provide photographic material containingat least one of said new photographic layers.

To accomplishthe foregoing objects and others which will hereinafter appear, our invention resides in the product and the method of producing same, as are more particularly described in the following specification and sought to be defined in the appended claims.

accordance with our invention, we produce colored photographic layers by using dyestufis corresponding to the following general mesomeric formula wherein R and R" are an aromatic residue,

A anclB are an auxochrome, I

X- is an organic acid residue, and L Y Z'is H, CN, CONH2, -COOH, --SH, either substituted or not.

These dyesalts may be prepared by mixing a solution of a base according to the general formula.A-R--CZOH--RB with a solution of an acid HX in a solvent which is miscible with the solvent of the base. In this way intensely colored solutions are obtained.

Bases according to the formula 27(1894) 3294); dialkylamino diphenyl glycolicacid amide (id) dialkylamino diphenyl glycolic acid (id.) dialkylamino thiobenzophenone (J Am. Chem. Soc. (1933) 2518) bases substituted by salt-forming groups, such as sulphonicgroups,

for instance, (Ber. 39(1906) 3773).

For the salt formation, among others, methylene disalicylic acid, methylene digallic acid, benzoic acid, oxybenzoic acid, phthalic acid may be used.

With a suitable choice of X1 these dyestuffs can form resinous layers without addition of e 3 4 binding agent, for instance, when X- is methtense-red colored solution is obtained which, ylenedisalicylate or methylenedigallate. Accordafter cooling and spreading out on a glass plate, ing to this invention, it is possible to disperse a dyesalt in an appropriate binding agent, for

instance, a borax shellac solution, a phenol con- Example 3 densation product of gelatine, and to coat therei 112 p p' tetmmethy1diamino benzhydrol Withdisulphonic acid and 72 g. methylene disalicylic The colored layers p p r d in c rd c with acid are dissolved in 4.6 litres ethyl alcohol. The

our invention excel in that they are quickly, 2 solution produces a blue anti-halation layer of the completely and irreversibly discolored in an alkaprobable general formula probable general formula CH COOH- COOH- 00o CH 0 3 cm HO line or acid medium, for instance, an ordinary Example 4 photographic developer. They are proof against 30 g p p, tetmmethy1 diamino diphenyl Co a W fingers and other mechanical 35 glycolic acid amide and 30 g. methylene disalicylic tacts, are usable e the With Without a binding acid are dissolved in 1.8 litres of ethyl alcohol. agent and they produce harmless decomposition The solution obtained produces, after cooling and products and possess an extraordinary density. spreading out on a glass plate, a gree t Some examples, which illustrate the present inhalation layer of the probable general formula COOH- C ONH2 E I CH3 0 O C H xo N/ C 2- 00 OH CH3 I CH3 HO OH CONH: 5 l 0 o c CH O OH j 0% h 0 CE: CH3 HO OH vention without limiting, however, in any way its scope are gwen heremaftergraphic purposes wherein colored layers are re- Example 1 quired, as filter layers, anti-halation layers, back '72 g. methylene disalicylic acid and 83 g. p-p'- layers and layers sensitive to light. These dyetetra-methyl diamino benzhydrol are dissolved in stuffs may as well be added to a light-sensitive 2 litres warm ethyl alcohol. After cooling and emulsion one can also use a mixture of these spreading out on a glass plate, an intense-blue colored resinous anti-halation layer according to 6 dyestufis Wlth other dyestuffs already known and the following probable general formula is ob- 0 used for the same p The above dyestuffs are suited for all phototained We claim:

CH3 CH3 o 0 c CH2 0 0 0H" N -CH= N\ oh: I CH3 HO OH C53 /CH3 +0 0 C CH 00 H- [M P 0 CH3 CH3 HO; 0H

Example 2 144 g. methylene disalicylic acid and 128 g. pmethoxy-p'-dimethylamino benzhydrol are dissolved in 6,8 litres warm ethyl alcohol. An in- 1. A photographic anti-halation element comprising a glass support, a light-sensitive layer on one face thereof, and a layer on the other face of the support, said second layer consisting of a dyeproduces a resinous anti-halation layer of the 5 6 stuff according to one of the following mesomeric one face thereof, and a layer on the other face of formulae: the support, said second layer consisting of a dye- 3 0 oo- -om -ooon- 0%: T CHa HO OH 3 l :l ooo- CH2- -000H 2. A photographic anti-halation element comprising a glass support, a light-sensitive layer on stuff according to one of the following mesomeric formulae:

CONHz OH! I CH3 CONHz 053 i /CH:; 000-- CHs- COOH" N: H0 1 Cfia CH3 5. A photographic anti-halation element comprising a glass support, a light-sensitive layer on one face thereof, and a layer on the other face of the support, said second layer consisting of a dyel 9 HO- O one face thereof, and a layer on the other face of the support, said second layer consisting of a dyestuff according tonne of the following mesomeric formulae:

3. A photographic anti-halation elementcomprising a glass support, a light-sensitive layer on stuff according to one of the following mesomeric formulae:

wherein R and R represent phenylene, A and B represent a member selected from the group consisting of dialkylamino and alkoxy, and Z represents a member selected from the group con- COO- one face thereof, and a layer on the other face of the support, said second layer consisting of a dyestuff according to one of the following mesomeric formulae: 55 sisting of H and CONHz.

E "000-- 011,- OOOH- N- CH: N

0Q, Q Q CHa HO- OH sou; son: 7

CH3 1 OH:

Ca CHa HO- OH SOaH 03H 4. A photographic anti-halation element comprising a glass support, a light-sensitive layer on LAURENT ALOYS VAN DER AUWERA. ANDRE EMILE VAN DORMAEL. REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,036,546 Schneider Apr. 7, 1936 2,186,731 Schneider Jan. 9, 1940 

5. A PHOTOGRAPHIC ANTI-HALATION ELEMENT COMPRISING A GLASS SUPPORT, A LIGHT-SENSITIVE LAYER ON ONE FACE THEREOF, AND A LAYER ON THE OTHER FACE OF THE SUPPORT, SAID SECOND LAYER CONSISTING OF A DYESTUFF ACCORDING TO ONE OF THE FOLLOWING MESOMERIC FORMULAE: 